6h-indeno[2,1-b]quinoline derivative and organic light emitting diode using the same

ABSTRACT

A 6H-indeno[2,1-b]quinoline derivative has a structure of formula (I). Each of Ar 1  and Ar 2  is a member selected from the group consisting of a substituted or non-substituted aryl group and a substituted or non-substituted heteroaryl group and R 1  to R 9  are substituents. The 6H-indeno[2,1-b]quinoline derivative of the present invention is provided with thermal stability. Chemical compounds of the present invention are adequate for the materials of the light-emitting layer of an OLED device with high device performance.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a chemical compound and an organiclight emitting diode (OLED), and more particularly to a6H-indeno[2,1-b]quinoline derivative and organic light emitting diodeusing the same.

2. Description of the Prior Art

OLED is composed of organic materials and semiconductor materials. OLEDworks on the mechanism that electrons and holes diffuse through anelectron transport layer (ETL) and hole transport layer (HTL)respectively to enter a light-emitting layer, and recombine in theemitting region to form excitons. When excitons fall to the groundstate, the energy is given off in the form of photo radiation. Theradiation color can be tuned by applying different emitting materials.OLED has been spotlighted due to a lot of advantages, such as selfillumination, wider visual angle (>170°), shorter response time (˜μs),higher contrast, higher efficiency, lower power consumption, higherbrightness, lower operative voltage (3-10V), thinner size (<2 mm),flexibility and so on.

Excitons generated from recombining holes and electrons have tripletstate or singlet state for its spin state. Singlet exciton relaxationradiates fluorescence and triplet exciton relaxation radiatesphosphorescence. Phosphorescence achieves 3-fold efficiency comparing tofluorescence and may greatly enhance the IQE (internal quantumefficiency) of devices up to 100% by adopting metal complexes inelectroluminescent configuration to achieve strong spin-orbital couplingand mixing of singlets and triplets. Therefore, phosphorescent metalcomplexes are now adopted as phosphorescent dopants in the emittinglayer of OLED. In addition, by doping proper materials to thelight-emitting layer, self-quenching of the host materials can bereduced greatly to enhance the efficiency of the OLED device. Withrespect to host materials, they must be capable of catching carrierseasily and have high photoelectric conversion performance, high thermalstability and proper band gap of singlet state and triplet state.

To sum up, it is an important issue to develop a novel host material tobe applied in OLED.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a novel chemicalcompound with high thermal stability to be applied in OLED.

According to one embodiment of the present invention, a6H-indeno[2,1-b]quinoline derivative has a structure of formula (I):

wherein each of Ar₁ and Ar₂ is a member selected from the groupconsisting of a substituted or non-substituted aryl group and asubstituted or non-substituted heteroaryl group; each of substituents R₁to R₉ is a member independently selected from the group consisting of H,halo, cyano, amino, substituted or non substituted C₁-C₁₀ alkyl,substituted or non substituted C₂-C₁₀ alkenyl, substituted or nonsubstituted C₂-C₁₀ alkynyl, substituted or non substituted C₃-C₂₀cycloalkyl, substituted or non substituted C₃-C₂₀ cycloalkenyl,substituted or non substituted C₁-C₂₀ heterocycloalkyl, substituted ornon substituted C₁-C₂₀ heterocycloalkenyl, substituted or nonsubstituted aryl and substituted or non substituted heteroaryl.

It is another object of the present invention to provide an organiclight emitting diode with high device performance.

According to another embodiment of the present invention, an organiclight emitting diode comprising a cathode, an anode and a light-emittinglayer arranged between the anode and the cathode. The light-emittinglayer comprises the aforementioned 6H-indeno[2,1-b]quinoline derivative.

The objective, technologies, features and advantages of the presentinvention will become apparent from the following description inconjunction with the accompanying drawings wherein certain embodimentsof the present invention are set forth by way of illustration andexample.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a schematic diagram illustrating the structure of anorganic light-emitting diode using the 6H-indeno[2,1-b]quinolinederivative.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The 6H-indeno[2,1-b]quinoline derivative has the structure of formula(I) to (IX) according to the present invention:

wherein each of Ar₁ and Ar₂ is a member selected from the groupconsisting of a substituted or non-substituted aryl group and asubstituted or non-substituted heteroaryl group; each of substituents R₁to R₉ is a member independently selected from the group consisting of H,halo, cyano, amino, substituted or non substituted C₁-C₁₀ alkyl,substituted or non substituted C₂-C₁₀ alkenyl, substituted or nonsubstituted C₂-C₁₀ alkynyl, substituted or non substituted C₃-C₂₀cycloalkyl, substituted or non substituted C₃-C₂₀ cycloalkenyl,substituted or non substituted C₁-C₂₀ heterocycloalkyl, substituted ornon substituted C₁-C₂₀ heterocycloalkenyl, substituted or nonsubstituted aryl and substituted or non substituted heteroaryl.

The term “aryl” refers to a hydrocarbon moiety having one or morearomatic rings. Examples of aryl moieties include phenyl (Ph),phenylene, naphthyl, naphthylene, pyrenyl, anthryl, and phenanthryl.

The term “heteroaryl” refers to a moiety having one or more aromaticrings that contain at least one heteroatom (e.g., N, O, or S). Examplesof heteroaryl moieties include furyl, furylene, fluorenyl, pyrrolyl,thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl,quinazolinyl, quinolyl, isoquinolyl and indolyl.

Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl,heterocycloalkenyl, aryl, and heteroaryl mentioned herein include bothsubstituted and unsubstituted moieties, unless specified otherwise.Possible substituents on cycloalkyl, cycloalkenyl, heterocycloalkyl,heterocycloalkenyl, aryl, and heteroaryl include, but are not limitedto, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, C₃-C₂₀ cycloalkyl,C₃-C₂₀ cycloalkenyl, C₁-C₂₀ heterocycloalkyl, heterocycloalkenyl,alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, amino, C₁-C₁₀alkylamino, dialkylamino, arylamino, diarylamino, C₁-C₁₀alkylsulfonamino, arylsulfonamino, alkylimino, arylimino, C₁-C₁₀alkylsulfonimino, arylsulfonimino, hydroxyl, halo, thio, alkylthio,arylthio, C₁-C₁₀ alkylsulfonyl, arylsulfonyl, acylamino, aminoacyl,aminothioacyl, amido, amidino, guanidine, ureido, thioureido, cyano,nitro, nitroso, azido, acyl, thioacyl, acyloxy, carboxyl, and carboxylicester. On the other hand, possible substituents on alkyl, alkenyl, oralkynyl include all of the above-recited substituents except C₁-C₁₀alkyl. Cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl,aryl, and heteroaryl can also be fused with each other.

TABLE 1 chemical compounds according to embodiments of the presentinvention. NO. acronym Chemical formula 1 BPhIDQ

2 TolCzPhIDQ

3 Tol2NPhPHIDQ

4 BCzIDQ

5 BTPAIDQ

6 TolCzdiIDQ

7 TolNPh2diIDQ

Please refer to the following description illustrating the syntheticpathway of the 6H-indeno[2,1-b]quinoline derivatives according to Table1 of the present invention.

Compound Synthesis

Chemical compounds can be obtained by performing nucleophilic additionreactions twice between starting materials and different anilinearomatic rings (e.g. carbazole or triphenylamine) along with usingnon-metal catalytic Eaton's reagents on different chemical equivalentbasis.

Synthesis of 10-phenyl-11H-indeno[1,2-b]quinolin-11-one

The 6H-indeno[2,1-b]quinoline derivative of the present invention can besynthesized at high percentage yield by performing non-metal catalyticFriedlämder reaction to obtain derivatives containing quinolin andketone. The starting materials 1H-indene-1,3(2H)-dione (307 mg, 1.00 m),2-amonobenzophenone (400 mg, 2.00 mmol), diphenyl phosphate (DPP, 751mg, 3.00 mmol) and just-evaporated m-cresol are mixed in a round bottomflask and heated to 140° C. for two hours under nitrogen atmosphere.After reaction, 10% triethylamine/methanol is added into the crudeproduct and then filtered to remove precipitates. Finally,10-phenyl-11H-indeno[1,2-b]quinolin-11-one, appearing yellow, isseparated from the mixture by using column chromatography withN-hexane:ethyl acetate 10:1. The percentage yield is 81.3%.10-phenyl-11H-indeno[1,2-b]quinolin-1′-one obtained here can be alsoused as starting materials to produce other 6H-indeno[2,1-b]quinolinederivatives.

¹H NMR (400 MHz, CDCl₃, δ): 7.39-7.50 (m, 4H), 7.54-7.56 (m, 3H),7.64-7.75 (m, 4H), 8.10-8.15 (m, 2H); ¹³C NMR (100 MHz, CDCl₃, δ):121.7, 122.8, 1238, 127.0, 127.7, 128.1, 128.6, 128.9, 129.3, 129.9,131.6, 131.7, 132.9 135.3 137.5, 143.3, 148.1, 150.4, 162.0, 190.3; HRMS(EI, m/z): [M⁺] calcd for C₂₂H₁₃NO, 307.0997. found, 307.1001.

Synthesis of10-phenyl-11,11-bis(9-phenyl-9H-carbazol-3-yl)-11H-indeno[1,2-b]quinoline

The chemical compound can be obtained by performing nucleophilicaddition reactions twice between starting materials and differentaniline aromatic rings (e.g. carbazole or triphenylamine) along withusing non-metal catalytic Eaton's reagents on different chemicalequivalent basis. First, 10-phenyl-1H-indeno[1,2-b]quinolin-11-one (860mg, 2.80 mmol) and 9-phenyl-9H-carbazole (1500 mg, 6.10 mmol) are placedin a round bottom flask and then dissolved in 5 ml of dichloromethane.Subsequently, 800 μl of Eaton's reagent is slowly dripped into the flaskto promote reaction. After 12 hours of reaction at 100° C., the crudeproduct is extracted with 20 ml of dichloromethane and sodiumbicarbonate for three times. Finally, an organic layer of the crudeproduct is dehydrated with magnesium sulfate and concentrated to besublimated and purified to obtain 1820 mg of10-phenyl-11,11-bis(9-phenyl-9H-carbazol-3-yl)-11H-indeno[1,2-b]quinoline.The percentage yield is 83.8%.

¹H NMR (400 MHz, CDCl₃, δ): 6.59 (d, 1H, J=7.6 Hz), 6.82 (dd, 2H, J=7.6,7.2 Hz), 7.04-7.18 (m, 4H), 7.22-7.26 (m, 1H), 7.28-7.46 (m, 6H),7.52-7.59 (m, 4H), 7.67-7.73 (m, 2H), 7.79 (d, 1H, J=7.6 Hz), 8.27 (d,1H. J=8.0 Hz), 8.33 (d, 1H, J=7.2 Hz); ¹³C NMR (100 MHz, CDCl₃, δ):64.1, 109.0, 109.7, 119.7, 120.6, 120.9, 121.9, 122.7, 123.4, 125.6,125.7, 125.8, 126.5, 126.8, 127.1, 127.3, 127.4, 127.5, 127.7, 128.6,128.9, 129.1, 129.7, 129.8, 131.2, 135.0, 135.2, 137.7, 137.9, 139.5,141.0, 141.5, 145.2, 148.6, 157.2, 161.0; HRMS (EI, m/z): [M⁺] calcd forC₅₈H₃₇N₃, 775.2987. found, 775.2993. Anal. calcd. for C₅₈H₃₇N₃: C,89.78; H, 4.81; N, 5.42. found: C, 89.22; H, 4.99; N, 5.46.

Synthesis of4,4′-(10-phenyl-11H-indeno[1,2-b]quinoline-11,11-diyl)bis(N,N-di-p-tolylaniline

Referring to the reaction formula above,10-phenyl-11H-indeno[1,2-b]quinolin-11-one (860 mg, 2.80 mmol) and4-methyl-N-phenyl-N-(p-tolyl)aniline (1668 mg, 6.10 mmol) are placed ina round bottom flask and then dissolved in 5 ml of dichloromethane.Subsequently, 800 μl of Eaton's reagent is slowly dripped into the flaskto promote reaction. After 12 hours of reaction at 100° C., the crudeproduct is extracted with 20 ml of dichloromethane and sodiumbicarbonate for three times. Finally, an organic layer of the crudeproduct is dehydrated with magnesium sulfate and concentrated to besublimated and purified to obtain 2050 mg of10-phenyl-11,11-bis(9-phenyl-9H-carbazol-3-yl)-11H-indeno[1,2-b]quinoline.The percentage yield is 87.6%.

¹H NMR (400 MHz, CDCl₃, δ): 2.26 (s, 12H), 6.63-6.75 (m, 10H), 6.90 (d,8H, J=8.0 Hz), 7.00 (d, 8H, J=7.6 Hz), 7.15 (dd, 2H, J=8.0, 7.6 Hz),7.26-7.35 (m, 4H), 7.36 (dd, 1H, J=7.6, 7.2 Hz), 7.42 (dd, 1H, J=8.0,7.2 Hz), 7.66 (ddd, 1H, J=7.6, 7.2, 0.8 Hz), 8.20 (d, 1H, J=7.6 Hz),8.25 (d, 1H, J=7.2 Hz); ¹³C NMR (100 MHz, CDCl₃, δ): 20.7, 62.8, 121.8,122.0, 124.2, 125.6, 126.4, 127.4, 127.5, 127.6, 128.5, 129.0, 129.5,129.7, 130.1, 131.1, 132.2, 135.2, 136.1, 138.0, 141.0, 144.5, 145.3,146.3, 148.5, 156.2, 160.7; FIRMS (EI, m/z): [M⁺] calcd for C₆₁H₄₇N₃,835.3926. found, 835.3934. Anal. calcd. for C₆₁H₄₇N₃: C, 89.13; H, 5.76;N, 5.11. found: C, 89.42; H, 5.75; N, 4.71.

Synthesis of 10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-ol

After dripping 1M phenylmagnesium bromide (20 ml, 20.0 mmol) into thestarting material 10-phenyl-1H-indeno[1,2-b]quinolin-11-one (3.07 g,10.0 mmol) which is dissolved in pure tetrahydrofuran, the mixedsolution undergoes reaction for 24 hours at room temperature. Then, thereaction is terminated by adding ammonium chloride solution therein.Finally, 3.47 g of 10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-ol isobtained by filtering the mixed solution to remove precipitates. Thepercentage yield is 90.0%. 10-diphenyl-1H-indeno[1,2-b]quinolin-1′-olobtained here can be also used as starting materials to produce other6H-indeno[2,1-b]quinoline derivatives.

HRMS (EI, m/z): [M⁺] calcd for C₂₈H₁₉NO, 385.1467. found, 385.1472.

Synthesis of10,11-diphenyl-11-(9-(p-tolyl)-9H-carbazol-3-yl)-11H-indeno[1,2-b]quinoline

Referring to the reaction formula above,10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-ol (385 mg, 1.00 mmol) and9-(p-tolyl)-9H-carbazole (291 mg, 1.20 mmol) are placed in a roundbottom flask and then dissolved in 5 ml of dichloromethane.Subsequently, 286 of Eaton's reagent is slowly dripped into the flask topromote reaction. After 12 hours of reaction at 100° C., the crudeproduct is extracted with 8 ml of dichloromethane and sodium bicarbonatefor three times. Finally, an organic layer of the crude product isdehydrated with magnesium sulfate and concentrated to be sublimated andpurified to obtain 521 mg of10,11-diphenyl-11-(9-(p-tolyl)-9H-carbazol-3-yl)-11H-indeno[1,2-b]quinoline.The percentage yield is 83.4%.

¹H NMR (400 MHz, CDCl₃, δ): 2.44 (s, 3H), 6.55 (d, 1H, J=8.0 Hz). 6.69(d, 1H, J=7.6 Hz), 6.83 (dd, 1H, J=7.6, 7.2 Hz), 7.25-7.47 (m. 20H),7.60 (d, 1H, J=1.2 Hz), 7.70 (ddd, 1H, J=8.4, 7.6, 20 Hz), 7.81 (d, 1H,J=7.6 Hz), 8.29 (d, 1H, J=8.4 Hz), 8.34 (d, 1H, J=7.6 Hz); ¹³C NMR (100MHz, CDCl₃, δ): 21.2, 64.0, 108.9, 109.7, 129.5, 120.5, 120.9, 121.9,122.5, 123.2, 125.6, 125.7, 126.4, 126.5, 126.6, 126.9, 127.3, 127.4,127.5, 127.6, 127.7, 128.5, 128.8, 128.9, 129.1, 129.6, 129.7, 130.4,131.2, 134.2, 134.9, 135.0, 137.2, 138.0, 139.6, 141.0, 141.2, 143.8,145.1, 148.6, 156.7, 160.8; HRMS (EI, m/z): [M⁺] calcd for C₄₇H₃₂N₂,624.2565. found, 624.2557. Anal. calcd. for C₄₇H₃₂N₂: C, 90.35; H, 5.16;N, 4.48. found: C, 89.85; H, 5.49; N, 4.11.

Synthesis of11,11′-(9-(p-tolyl)-9H-carbazole-3,6-diyl)bis(10,11-diphenyl-11H-indeno[1,2-b]quinoline

The products of the present invention can be obtained via the reactionbetween starting materials and different aniline aromatic rings. In anembodiment, the starting material10,11-diphenyl-1H-indeno[1,2-b]quinolin-11-ol (963 mg, 2.50 mmol) and9-(p-tolyl)-9H-carbazole (257 mg, 1.00 mmol) are placed in a roundbottom flask and then dissolved in 10 ml of dichloromethane.Subsequently, trifluoromethanesulfonic acid (0.27 ml, 3.0 mmol) isslowly dripped into the flask to promote reaction. After 12 hours ofreaction at 140° C., the crude product is extracted with 50 ml of Ethylacetate and sodium bicarbonate for three times. Finally, an organiclayer of the crude product is dehydrated with magnesium sulfate andconcentrated to be sublimated and purified to obtain 670 mg of11,11′-(9-(p-tolyl)-9H-carbazole-3,6-diyl)bis(10,11-diphenyl-11H-indeno[1,2-b]quinoline.The percentage yield is 67.6%.

¹H NMR (400 MHz, CDCl₃, δ): 2.41 (s, 3H), 6.46-6.52 (m, 3H), 6.60 (d,1H, J=6.0 Hz), 6.73-682 (m, 4H), 6.87-7.10 (m, 17H), 7.19-7.35 (m, 14H),7.39-7.45 (m, 2H), 7.65-7.70 (m, 2H), 8.22-8.33 (m, 3H); ¹³C NMR (100MHz, CDCl₃, δ): 21.1, 63.9, 108.7, 108.9, 120.9, 121.0, 121.8, 122.4,122.5, 125.6, 125.7, 126.3, 126.4, 126.5, 126.8, 126.9, 127.2, 127.3,127.3, 127.4, 127.5, 127.7, 127.8, 128.4, 128.5, 128.7, 128.8, 128.9,129.2, 129.5, 129.6, 139.9, 139.3, 139.3, 131.2, 131.3, 133.7, 134.0,134.7, 134.8, 134.9, 135.0, 137.1, 138.0, 139.7, 139.8, 140.9, 141.0,143.7, 143.9, 145.1, 145.2, 148.5, 156.6, 156.7, 160.6, 160.7; HRMS (EI,m/z): [M⁺] calcd for C₇₅H₄₉N₃, 991.3926. found, 991.3933. Anal. calcd.for C₇₅H₄₉N₃: C, 90.79, H, 4.98, N, 4.23. found: C, 90.30; H, 4.69; N,4.23.

Synthesis of4-(10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-yl)-N,N-di-p-tolylaniline

In an embodiment, the starting material10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-ol (385 mg, 1.00 mmol) and4-methyl-N-phenyl-N-(p-tolyl)aniline (328 mg, 1.20 mmol) are placed in around bottom flask and then dissolved in 10 ml of dichloromethane.Subsequently, trifluoromethanesulfonic acid (0.13 ml, 1.50 mmol) isslowly dripped into the flask to promote reaction. After 12 hours ofreaction at 140° C., the crude product is extracted with 50 ml of Ethylacetate and sodium bicarbonate for three times. Finally, an organiclayer of the crude product is dehydrated with magnesium sulfate andconcentrated to be sublimated and purified to obtain 575 mg of4-(10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-yl)-N,N-di-p-tolylaniline.The percentage yield is 89.7%.

¹H NMR (400 MHz, CDCl₃, δ): 2.66 (s, 6H), 6.59-6.70 (m, 61-1), 6.97 (d,4H, J=7.6 Hz), 7.20-7.26 (m, 10H), 7.28-7.46 (m, 7H), 7.68 (dd, 1H,J=6.8, 2.0 Hz), 8.22 (d, 1H, J=8.4 Hz), 8.26 (d, 1H, J=7.6 Hz); ¹³C NMR(100 MHz, CDCl₃, δ): 20.8, 63.3, 121.8, 121.9, 124.2, 125.6, 125.7,126.4, 127.5, 127.6, 127.7, 127.8, 128.4, 128.6, 129.0, 129.1, 129.5,129.6, 129.7, 130.0, 131.1, 132.2, 135.1, 135.7, 138.0, 140.8, 143.4,144.8, 145.3, 146.3, 148.6, 156.2, 160.7; HRMS (EI, m/z): [M⁺] calcd forC₄₈H₃₆N₂, 640.2878. found, 640.2880. Anal. calcd. for C₄₈H₃₆N₂: C,89.97, H, 5.66, N, 4.37. found: C, 89.70; H, 5.42; N, 3.98.

Syntehsis of4-(10,11-diphenyl-11H-[1,2-b]quinolin-11-yl)-N-(4-(10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-yl)phenyl)-N-(p-tolyl)aniline

In an embodiment, the starting material10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-ol (385 mg, 2.50 mmol) and4-methyl-N,N-diphenylaniline (259 mg, 1.00 mmol) are placed in a roundbottom flask and then dissolved in 10 ml of dichloromethane.Subsequently, trifluoromethanesulfonic acid (0.27 ml, 3.00 mmol) isslowly dripped into the flask to promote reaction. After 12 hours ofreaction at 140° C., the crude product is extracted with 50 ml of Ethylacetate and sodium bicarbonate for three times. Finally, an organiclayer of the crude product is dehydrated with magnesium sulfate andconcentrated to be sublimated and purified to obtain 699 mg of4-(10,11-diphenyl-11H-[1,2-b]quinolin-11-yl)-N-(4-(10,11-diphenyl-11H-indeno[1,2-b]quinolin-11-yl)phenyl)-N-(p-tolyl)aniline.The percentage yield is 70.3%.

¹H NMR (400 MHz, CDCl₃, δ): 6.66 (d, 2H, J=7.6 Hz), 6.99 (d, 4H, J=8.0Hz), 7.05-7.17 (m, 7H), 7.27-7.40 (m, 4H, J=7.2 Hz), 7.48 (t, 1H), 7.72(dd, 1H, J=8.0, 6.4 Hz), 8.33 (d, 1H, J=7.6 Hz), 8.38 (d, 1H, J=7.6 Hz);¹³C NMR (100 MHz, CDCl₃, δ): 20.8, 63.3, 121.9, 122.4, 122.5, 123.4,124.5, 125.6, 125.7, 126.4, 127.4, 127.5, 127.6, 128.1, 128.4, 128.5,128.6, 128.7, 129.0, 129.2, 129.6, 129.7, 129.8, 129.0, 130.0, 131.2,132.5, 132.6, 135.0, 135.1, 136.2, 137.9, 140.7, 143.2, 143.3, 144.9,146.0, 148.6, 156.0, 156.1, 160.7; HRMS (EI, m/z): [M⁺] calcd forC₇₅H₅₁N₃, 993.4083. found, 993.4075. Anal. calcd. for C₇₅H₅₁N₃: C,90.60; H, 5.17; N, 4.23. found: C, 86.82; H, 5.29; N, 408.

Synthesis of (10,11,11-triphenyl-11H-indeno[1,2-b]quinoline

In all embodiment, the starting material10,11-diphenyl-1H-indeno[1,2-b]quinolin-11-ol (385 mg, 2.50 mmol) andbenzene (1430 mg, 18.31 mmol) are placed in a round bottom flask andthen dissolved in 10 ml of dichloromethane. Subsequently,trifluoromethanesulfonic acid (0.09 ml, 1.10 mmol) is slowly drippedinto the flask to promote reaction. After 12 hours of reaction at 140°C., the crude product is extracted with 50 ml of Ethyl acetate andsodium bicarbonate for three times. Finally, an organic layer of thecrude product is dehydrated with magnesium sulfate and concentrated tobe sublimated and purified to obtain 281 mg of10,11,11-triphenyl-1H-indeno[1,2-b]quinoline. The percentage yield is91.7%.

¹H NMR (400 MHz, CDCl₃, δ): 6.57 (d, 2H, J=6.8 Hz), 6.88-6.91 (m, 4H),6.99-7.12 (m, 9H), 7.21-7.25 (m, 2H), 7.28-7.36 (m, 2H), 7.40-7.44 (m,1H), 7.64-7.70 (m, 1H), 8.22 (d, 1H, J=7.6 Hz), 8.27 (d, 1H, J=7.6 Hz);¹³C NMR (100 MHz, CDCl₃, δ): 6.38, 121.9, 125.5, 125.7, 126.4, 127.2,127.3, 127.6, 127.8, 128.4, 128.5, 128.7, 129.0, 129.2, 129.6, 131.2,135.0, 138.1, 140.4, 143.0, 145.0, 148.6, 156.0, 160.7; HRMS (EI, m/z):[M⁺] calcd for C₃₄H₂₃N, 445.1830. found, 445.1825. Anal. calcd. forC₃₄H₂₃N: C, 91.65; H, 5.20; N, 3.14. found: C, 91.50; H, 5.15; N, 2.72.

TABLE 2 properties of host materials using 6H-indeno[2,1-b]quinolinederivatives. host materials T_(g) (° C.) T_(d) (° C.) E_(g) (eV) E_(T)(eV) CBP 62 373 3.40 2.56 BPhIDQ 91 N/A 3.53 2.58 BCzIDQ 198 N/A 3.302.58 BTPAIDQ 151 N/A 3.17 2.58 TolCzPhIDQ 154 N/A 3.50 2.58 Tol2NPhPhIDQ133 N/A 3.25 2.58 TolCzdiIDQ 218 N/A 3.25 2.58 TolNPh₂diIDQ 196 N/A 3.102.58 T_(g): Glass transition temperature T_(d): DecompositionTemperature E_(g): Energy gap E_(T): Triplet energy

The Table 2 displays properties of host materials using6H-indeno[2,1-b]quinoline derivatives except thatCBP(4,4′-Bis(N-carbazolyl)-1,1′-biphenyl) is a control group. Comparingto CBP, the 6H-indeno[2,1-b]quinoline derivatives of the presentinvention have higher glass transition temperature (T_(g)) and thus havehigh thermal stability. Besides, different charge transport moieties canbe incorporated into the chemical compounds of the present inventionwithout changing its triplet state (approx. 2.58 eV), which can beapplied to red, orange or green emitting devices.

Besides, referring to the FIGURE, the FIGURE is a schematic diagramillustrating the structure of the organic light emitting diode using the6H-indeno[2,1-b]quinoline derivative as host materials according to anembodiment of the present invention. The organic light emitting diodecomprises an anode 1, a cathode 2 and a light-emitting layer 3 arrangedbetween the anode 1 and the cathode 2. The light-emitting layer 3comprises the chemical compounds provided by the present invention andis formed by doping light emitting materials into the host materials.The structure of the light-emitting materials also comprises a holetransport layer 4, an electron blocking layer 9, an light-emitting layer3, a hole blocking layer 6, an electron transporting layer 5 and anelectron injection layer 8 formed sequentially from bottom to top on theanode 1. Thickness of each layer displayed in the FIGURE is notrepresentative of actual size. Among these layers, the electron blockinglayer 9, the hole blocking layer 6, and the electron injection layer 8are optionally involved. The 6H-indeno[2,1-b]quinoline derivative of thepresent invention can be used as host materials or dopant of the lightemitting layer 3.

For example, the organic light emitting diode of the present inventioncan be a red phosphorescent OLED, a green phosphorescent OLED or aorange phosphorescent OLED.

Exemplified Electroluminescent Device Structure

Light emitting devices using different materials are exemplified herefor testing and comparing properties thereof. Among these devices, ITOis used as substrates; electrode materials comprises LiF/Al;light-emitting materials comprisesIr(piq)₃(Iridium(III)tris(1-phenyl-isoquinolinato-C2,N),Ir(ppy)₃(Iridium(III)Tris[2-phenylpyridinato-C2,N]),Ir(pq)₃(Iridium(III)tris[2-phenyl)-′C(quinolinyl-′N)); the electrontransport layer comprisesBCP(2,9-dimethyl-4,7-diphenyl-[1,10]phenanthroline) and Alq3(tris(8-hydroxyquinoline)aluminum(III), which are also adequate forelectron blocking layer or for both; hole transport layer comprises NPB(4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl) and TCTA(4,4′,4″-tri(N-carbazolyl)triphenylamine)), which are also adequate forelectron blocking layer or for both.

Comparison Between Device Performance

TABLE 3 properties of green OLED. (device configuration: NPB (20)/TCTA(10)/7% Ir (ppy)₃: Host material (30)/BCP (10)/Alq (40)/LiF (1)) V_(d)^(*a) η_(ext) ^(*b) L^(*c) η_(c) ^(*d) η_(p) ^(*e) λ_(em) ^(*f) CIE, 8VDevice [V] [%, V] [cd/m², V] [cd/A, V] [lm/W, V] [nm] (x, y) CBP 2.822.9, 4.5 163089, 15.5 64.7, 4.5 64.2, 3.0 586 (0.56, 0.44) BCzIDQ 2.825.8, 3.0 118075, 17.0 68.4, 3.0 71.7, 3.0 588 (0.57, 0.43) BTPAIDQ 2.317.2, 3.5  67583, 15.0 44.2, 3.5 53.4, 2.5 588 (0.57, 0.43) TolCzPhIDQ2.7 21.5, 3.5  88155, 17.5 58.6, 3.5 60.2, 3.0 584 (0.58, 0.44)Tol2NPhPhIDQ 2.5 16.7, 5.5 112054, 15.0 50.3, 5.5 38.2, 3.5 580 (0.54,0.45) TolCzdiIDQ 3.2 26.2, 5.0  93286, 18.0 67.9, 5.5 48.9, 4.0 590(0.57, 0.43) ^(*a)V_(d): drive voltage ^(*b)η_(ext): maximum externalquantum efficiency ^(*c)L: maximum luminescence ^(*d)η_(c): maximumcurrent efficiency ^(*e)η_(p): maximum power efficiency ^(*f)λ_(em):maximum emission wavelength

TABLE 4 properties of orange OLED. (device configuration: NPB (20)/TCTA(10)/4% Ir (pq)3: host material (30)/BCP (15)/Alq (50)/LiF (1)) Vdη_(ext) L η_(c) η_(p) λ_(em) CIE, 8V Device [V] [%, V] [cd/m², V] [cd/A,V] [lm/W, V] [nm] (x, y) CBP 2.8 22.9, 4.5 163089, 15.5 64.7, 4.5 64.2,3.0 586 (0.56, 0.44) BCzIDQ 2.8 25.8, 3.0 118075, 17.0 68.4, 3.0 71.7,3.0 588 (0.57, 0.43) BTPAIDQ 2.3 17.2, 3.5  67583, 15.0 44.2, 3.5 53.4,2.5 588 (0.57, 0.43) TolCzPhIDQ 2.7 21.5, 3.5  88155, 17.5 58.6, 3.560.2, 3.0 584 (0.58, 0.44) Tol2NPhPhIDQ 2.5 16.7, 5.5 112054, 15.0 50.3,5.5 38.2, 3.5 580 (0.54, 0.45) TolCzdiIDQ 3.2 26.2, 5.0  93286, 18.067.9, 5.5 48.9, 4.0 590 (0.57, 0.43)

TABLE 5 properties of red OLED. (device configuration: NPB (20)/TCTA(10)/4% Ir (piq)3: host material (30)/BCP (15)/Alq (50)/LiF (1)) Vdη_(ext) L η_(c) η_(p) λ_(em) CIE, 8V Device [V] [%, V] [cd/m², V] [cd/A,V] [lm/W, V] [nm] (x, y) CBP 3.1 18.2, 5.0 56041, 15.0 24.6, 5.0 21.5,3.5 620 (0.66, 0.34) BCzIDQ 3.1 24.3, 3.5 53322, 17.5 30.4, 3.5 27.3,3.5 620 (0.67, 0.33) BTPAIDQ 2.6 18.7, 5.0 47469, 15.0 23.7, 5.0 23.0,3.0 618 (0.67, 0.33) TolCzPhIDQ 3.0 23.4, 3.0 44574, 19.5 33.5, 3.035.0, 3.5 616 (0.66, 0.34) Tol2NPhPhIDQ 2.6 17.2, 5.5 57032, 14.0 23.2,5.5 18.7, 3.0 618 (0.66, 0.34) TolCzdiIDQ 3.2 23.4, 4.0 40921, 17.026.6, 4.0 23.6, 3.5 622 (0.67, 0.33)

TABLE 6 properties of green OLED. (device configuration: NPNPB 60/NPB(10)/TCTA (10)/7% Ir (ppy)3: host material (30)/BAlq (30)/LiF (1)) T₇₅ @L, 10V η_(ext) η_(c), 10V λ_(em), 8V FWHM^(*a) CIE, 8V 500 nits Device[cd/m²] [%, 10V] [cd/A] [nm] [nm] (x, y) (h) CBP 7819 13.9 50.4 510 54(0.24, 0.62) 2331 BCzIDQ 10937 15.8 60.5 514 58 (0.26, 0.66) 1592BTPAIDQ 27662 11.6 42.1 510 54 (0.26, 0.64) 28 TolCzPhIDQ 7144 9.8 36.7512 60 (0.28, 0.64) 116 Tol2NPhPhIDQ 21849 8.9 32.0 510 56 (0.27, 0.63)85 TolCzdiIDQ 23150 9.8 37.0 513 62 (0.28, 0.64) 6 ^(a)FWHM: full widthat half maximum

TABLE 7 properties of green OLED. (device configuration: NPNPB60/NPB(10)/TCTA(10)/7% Ir(ppy)3:host material(30)/BAlq(30)/LiF(1))Current V, density η_(ext) η_(c) η_(p) 500 [mA/cm², [%, [cd/A, [lm/w,Device nits 500 nits] 500 nits] 500 nits] 500 nits] CBP 6.9 1.213 11.441.1 18.5 BCzIDQ 6.3 0.713 18.4 70.2 35.1 BTPAIDQ 5.6 1.079 12.6 45.925.7 TolCzPhIDQ 6.7 1.339 10.0 37.2 17.6 Tol2NPhPhIDQ 5.6 1.388 10.035.9 20.2 TolCzdiIDQ 5.7 0.969 13.9 52.2 29.1

TABLE 8 properties of orange OLED. (device configuration: NPNPB 60/NPB(10)/TCTA (10)/4% Ir (pq)3: host material (30)/BAlq (30)/LiF (1)) T₇₅ @L, 10V η_(ext) η_(c), 10V λ_(em), 8V FWHM CIE, 8V 500 nits Device[cd/m²] [%, 10V] [cd/A] [nm] [nm] (x, y) (h) CBP 7082 12.2 37.1 580 62(0.54, 0.46) 2415 BPhIDQ 4677 16.3 44.0 584 78 (0.56, 0.44) 2809 BCzIDQ3278 14.5 40.0 582 64 (0.55, 0.45) 955 BTPAIDQ 18565 10.0 27.4 582 74(0.55, 0.74) 18 TolCzPhIDQ 6963 15.3 40.9 588 76 (0.57, 0.43) 2520Tol2NPhPhIDQ 18459 11.3 32.2 580 72 (0.55, 0.45) 472

TABLE 9 properties of orange OLED. (device configuration: NPNPB60/NPB(10)/TCTA(10)/4% Ir(pq)3: host materials(30)/BAlq(30)/LiF(1))Current V, density η_(ext) η_(c) η_(p) 500 [mA/cm², [%, [cd/A, [lm/w,Device nits 500 nits] 500 nits] 500 nits] 500 nits] CBP 6.7 1.156 14.143.1 20.3 BPhIDQ 6.9 0.963 19.3 52.0 23.8 BCzIDQ 8.0 1.006 16.8 49.819.5 BTPAIDQ 5.9 1.497 12.0 33.2 17.8 TolCzPhIDQ 6.2 1.018 18.4 49.024.9 Tol2NPhPhIDQ 5.6 1.340 13.0 37.1 20.8

TABLE 10 properties of green OLED. (device configuration: NPNPB 60/NPB(10)/TCTA (10)/4% Ir (piq)3: host material (30)/BAlq (30)/LiF (1))λ_(em), T₇₅ @ L, 10V η_(ext) η_(c),10V 8V FWHM CIE, 8V 500 nits Device[cd/m²] [%, 10V] [cd/A] [nm] [nm] (x, y) (h) CBP 1027 1.6  0.9 620 52(0.62, 0.33) 97 BPhIDQ 1635 14.4 17.8 618 58 (0.67, 0.33) 254 BCzIDQ1015 12.3 16.5 616 52 (0.66, 0.34) 92 BTPAIDQ 6745 13.0 15.8 620 54(0.67, 0.33) 14 TolCzPhIDQ 2120 14.5 17.9 620 60 (0.67, 0.33) 222Tol2NPhPhIDQ 9645 11.9 15.7 618 54 (0.66, 0.33) 75

TABLE 11 properties of red OLED(device configuration: NPNPB(60)/NPB(10)/TCTA(10)/4% Ir(piq)3:host material(30)/BAlq(30)/LiF(1))Current V, density η_(ext) η_(c) η_(p) 500 [mA/cm², [%, [cd/A, [lm/w,Device nits 500 nits] 500 nits] 500 nits] 500 nits] CBP 13.3 8.396 4.76.0 1.4 BPhIDQ 8.4 2.505 16.2 20.0 7.5 BCzIDQ 9.0 2.813 13.2 17.8 6.2BTPAIDQ 7.0 2.670 15.3 18.7 8.5 TolCzPhIDQ 7.7 2.481 16.4 20.2 8.2Tol2NPhPhIDQ 6.7 2.702 14.0 18.5 8.7

Referring to Table 3 to Table 11, it shows performance of green, orangeand red light-emitting devices. It is noted that the red and orangelight-emitting device using the compounds of the present invention ashost material have longer device life under 500 nit.

In conclusion, the 6H-indeno[2,1-b]quinoline derivative of the presentinvention is provided with high thermal stability and can be applied inthe light-emitting layer of an OLED device to achieve high deviceperformance.

While the invention is susceptible to various modifications andalternative forms, a specific example thereof has been shown in thedrawings and is herein described in detail. It should be understood,however, that the invention is not to be limited to the particular formdisclosed, but to the contrary, the invention is to cover allmodifications, equivalents, and alternatives falling within the spiritand scope of the appended claims.

What is claimed is:
 1. A 6H-indeno[2,1-b]quinoline derivative having astructure of formula (I):

wherein each of Ar₁ and Ar₂ is a member selected from the groupconsisting of a substituted or non-substituted aryl group and asubstituted or non-substituted heteroaryl group; each of substituents R₁to R₉ is a member independently selected from the group consisting of H,halo, cyano, amino, substituted or non substituted C₁-C₁₀ alkyl,substituted or non substituted C₂-C₁₀ alkenyl, substituted or nonsubstituted C₂-C₁₀ alkenyl, substituted or non substituted C₃-C₂₀cycloalkyl, substituted or non substituted C₃-C₂₀ cycloalkenyl,substituted or non substituted C₁-C₂₀ heterocycloalkyl, substituted ornon substituted C₁-C₂₀ heterocycloalkenyl, substituted or nonsubstituted aryl and substituted or non substituted heteroaryl.
 2. The6H-indeno[2,1-b]quinoline derivative according to claim 1 having astructure of formula (II):

wherein each of substituents R₁₀ to R₁₄ is a member independentlyselected from the group consisting of H, halo, cyano, amino, substitutedor non substituted C₁-C₁₀ alkyl, substituted or non substituted C₂-C₁₀alkenyl, substituted or non substituted C₂-C₁₀ alkynyl, substituted ornon substituted C₃-C₂₀ cycloalkyl, substituted or non substituted C₃-C₂₀cycloalkenyl, substituted or non substituted C₁-C₂₀ heterocycloalkyl,substituted or non substituted C₁-C₂₀ heterocycloalkenyl, substituted ornon substituted aryl and substituted or non substituted heteroaryl. 3.The 6H-indeno[2,1-b]quinoline derivative according to claim 1 having astructure of formula (III):


4. The 6H-indeno[2,1-b]quinoline derivative according to claim 1 havinga structure of formula (IV):

wherein each of substituents R₁₀ to R₁₄ is a member independentlyselected from the group consisting of H, halo, cyano, amino, substitutedor non substituted C₁-C₁₀ alkyl, substituted or non substituted C₂-C₁₀alkenyl, substituted or non substituted C₂-C₁₀ alkynyl, substituted ornon substituted C₃-C₂₀ cycloalkyl, substituted or non substituted C₃-C₂₀cycloalkenyl, substituted or non substituted C₁-C₂₀ heterocycloalkyl,substituted or non substituted C₁-C₂₀ heterocycloalkenyl, substituted ornon substituted aryl and substituted or non substituted heteroaryl. 5.The 6H-indeno[2,1-b]quinoline derivative according to claim having astructure of formula (V):


6. The 6H-indeno[2,1-b]quinoline derivative according to claim 1 havinga structure of formula (VI) or formula (VII):


7. The 6H-indeno[2,1-b]quinoline derivative according to claim 1 havinga structure of formula (VIII) or formula (IX):

wherein each of substituents R₁₅ to R₁₇ is a member independentlyselected from the group consisting of H, halo, cyano, amino, substitutedor non substituted C₁-C₁₀ alkyl, substituted or non substituted C₂-C₁₀alkenyl, substituted or non substituted C₂-C₁₀ alkynyl, substituted ornon substituted C₃-C₂₀ cycloalkyl, substituted or non substituted C₃-C₂₀cycloalkenyl, substituted or non substituted C₁-C₂₀ heterocycloalkyl,substituted or non substituted C₁-C₂₀ heterocycloalkenyl, substituted ornon substituted aryl and substituted or non substituted heteroaryl. 8.An organic light emitting diode comprising: a cathode; an anode; and alight-emitting layer arranged between the anode and the cathode, whereinthe light-emitting layer comprises a 6H-indeno[2,1-b]quinolinederivative.
 9. The organic light emitting diode according to claim 8,wherein the 6H-indeno[2,1-b]quinoline derivative has a structure offormula (I):

wherein each of Ar₁ and Ar₂ is a member selected from the groupconsisting of a substituted or non-substituted aryl group and asubstituted or non-substituted heteroaryl group; each of substituents R₁to R₉ is a member independently selected from the group consisting of H,halo, cyano, amino, substituted or non substituted C₁-C₁₀ alkyl,substituted or non substituted C₂-C₁₀ alkenyl, substituted or nonsubstituted C₂-C₁₀ alkynyl, substituted or non substituted C₃-C₂₀cycloalkyl, substituted or non substituted C₃-C₂₀ cycloalkenyl,substituted or non substituted C₁-C₂₀ heterocycloalkyl, substituted ornon substituted C₁-C₂₀ heterocycloalkenyl, substituted or nonsubstituted aryl and substituted or non substituted heteroaryl.
 10. Theorganic light emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative has a structure of formula (II):

wherein each of substituents R₁₀ to R₁₄ is a member independentlyselected from the group consisting of H, halo, cyano, amino, substitutedor non substituted C₁-C₁₀ alkyl, substituted or non substituted C₂-C₁₀alkenyl, substituted or non substituted C₂-C₁₀ alkynyl, substituted ornon substituted C₃-C₂₀ cycloalkyl, substituted or non substituted C₃-C₂₀cycloalkenyl, substituted or non substituted C₁-C₂₀ heterocycloalkyl,substituted or non substituted C₁-C₂₀ heterocycloalkenyl, substituted ornon substituted aryl and substituted or non substituted heteroaryl. 11.The organic light emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative has a structure of formula (III):


12. The organic light emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative has a structure of formula (IV):

wherein each of substituents R₁₀ to R₁₄ is a member independentlyselected from the group consisting of H, halo, cyano, amino, substitutedor non substituted C₁-C₁₀ alkyl, substituted or non substituted C₂-C₁₀alkenyl, substituted or non substituted C₂-C₁₀ alkynyl, substituted ornon substituted C₃-C₂₀ cycloalkyl, substituted or non substituted C₃-C₂₀cycloalkenyl, substituted or non substituted C₁-C₁₀ heterocycloalkyl,substituted or non substituted C₁-C₁₀ heterocycloalkenyl, substituted ornon substituted aryl and substituted or non substituted heteroaryl. 13.The organic light emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative has a structure of formula (V):


14. The organic light emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative has a structure of formula (VI) orformula (VII):


15. The organic light emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative has a structure of formula (VIII)or formula (IX):

wherein each of substituents R₁₅ to R₁₇ is a member independentlyselected from the group consisting of H, halo, cyano, amino, substitutedor non substituted C₁-C₁₀ alkyl, substituted or non substituted C₂-C₁₀alkenyl, substituted or non substituted C₂-C₁₀ alkynyl, substituted ornon substituted C₃-C₂₀ cycloalkyl, substituted or non substituted C₃-C₂₀cycloalkenyl, substituted or non substituted C₁-C₂₀ heterocycloalkyl,substituted or non substituted C₁-C₂₀ heterocycloalkenyl, substituted ornon substituted aryl and substituted or non substituted heteroaryl. 16.The organic light emitting diode according to claim 8, wherein theorganic light emitting diode is a red phosphorescent OLED, a greenphosphorescent OLED or an orange phosphorescent OLED.
 17. The organiclight emitting diode according to claim 8, wherein the6H-indeno[2,1-b]quinoline derivative is a host material or a dopant.